New Supramolecular Hypoxia-Sensitive Complexes Based on Azo-Thiacalixarene
Hypoxia accompanies many human diseases and is an indicator of tumor aggressiveness. Therefore, measuring hypoxia in vivo is clinically important. Recently, complexes of calix[4]arene were identified as potent hypoxia markers. The subject of this paper is new hypoxia-sensitive host–guest complexes o...
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MDPI AG
2023-01-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/28/2/466 |
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| author | Farida Galieva Mohamed Khalifa Zaliya Akhmetzyanova Diana Mironova Vladimir Burilov Svetlana Solovieva Igor Antipin |
| author_facet | Farida Galieva Mohamed Khalifa Zaliya Akhmetzyanova Diana Mironova Vladimir Burilov Svetlana Solovieva Igor Antipin |
| author_sort | Farida Galieva |
| collection | DOAJ |
| description | Hypoxia accompanies many human diseases and is an indicator of tumor aggressiveness. Therefore, measuring hypoxia in vivo is clinically important. Recently, complexes of calix[4]arene were identified as potent hypoxia markers. The subject of this paper is new hypoxia-sensitive host–guest complexes of thiacalix[4]arene. We report a new high-yield synthesis method for thiacalix[4]arene with four anionic carboxyl azo fragments on the upper rim (thiacalixarene <b>L</b>) and an assessment of the complexes of thiacalixarene <b>L</b> with the most widespread cationic rhodamine dyes (6G, B, and 123) sensitivity to hypoxia. Moreover, 1D and 2D NMR spectroscopy data support the ability of the macrocycles to form complexes with dyes. Rhodamines B and 123 formed host–guest complexes of 1:1 stoichiometry. Complexes of mixed composition were formed with rhodamine 6G. The association constant between thiacalixarene <b>L</b> and rhodamine 6G is higher than for other dyes. Thiacalixarene <b>L</b>-dye complexes with rhodamine 6G and rhodamine B are stable in the presence of various substances present in a biological environment. The UV-VIS spectrometry and fluorescence showed hypoxia responsiveness of the complexes. Our results demonstrate that thiacalixarene <b>L</b> has a stronger binding with dyes compared with the previously reported azo-calix[4]arene carboxylic derivative. Thus, these results suggest higher selective visualization of hypoxia for the complexes with thiacalixarene <b>L</b>. |
| first_indexed | 2024-03-09T11:37:05Z |
| format | Article |
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| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-09T11:37:05Z |
| publishDate | 2023-01-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-78e73f306804401398402735592b22da2023-11-30T23:40:16ZengMDPI AGMolecules1420-30492023-01-0128246610.3390/molecules28020466New Supramolecular Hypoxia-Sensitive Complexes Based on Azo-ThiacalixareneFarida Galieva0Mohamed Khalifa1Zaliya Akhmetzyanova2Diana Mironova3Vladimir Burilov4Svetlana Solovieva5Igor Antipin6Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, 420088 Kazan, RussiaDepartment of Organic and Medical Chemistry, Kazan Federal University, 420008 Kazan, RussiaArbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, 420088 Kazan, RussiaDepartment of Organic and Medical Chemistry, Kazan Federal University, 420008 Kazan, RussiaDepartment of Organic and Medical Chemistry, Kazan Federal University, 420008 Kazan, RussiaArbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, 420088 Kazan, RussiaArbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, 420088 Kazan, RussiaHypoxia accompanies many human diseases and is an indicator of tumor aggressiveness. Therefore, measuring hypoxia in vivo is clinically important. Recently, complexes of calix[4]arene were identified as potent hypoxia markers. The subject of this paper is new hypoxia-sensitive host–guest complexes of thiacalix[4]arene. We report a new high-yield synthesis method for thiacalix[4]arene with four anionic carboxyl azo fragments on the upper rim (thiacalixarene <b>L</b>) and an assessment of the complexes of thiacalixarene <b>L</b> with the most widespread cationic rhodamine dyes (6G, B, and 123) sensitivity to hypoxia. Moreover, 1D and 2D NMR spectroscopy data support the ability of the macrocycles to form complexes with dyes. Rhodamines B and 123 formed host–guest complexes of 1:1 stoichiometry. Complexes of mixed composition were formed with rhodamine 6G. The association constant between thiacalixarene <b>L</b> and rhodamine 6G is higher than for other dyes. Thiacalixarene <b>L</b>-dye complexes with rhodamine 6G and rhodamine B are stable in the presence of various substances present in a biological environment. The UV-VIS spectrometry and fluorescence showed hypoxia responsiveness of the complexes. Our results demonstrate that thiacalixarene <b>L</b> has a stronger binding with dyes compared with the previously reported azo-calix[4]arene carboxylic derivative. Thus, these results suggest higher selective visualization of hypoxia for the complexes with thiacalixarene <b>L</b>.https://www.mdpi.com/1420-3049/28/2/466supramolecular chemistrythiacalixarenehypoxia sensinghost–guest complexcationic rhodamine dyes |
| spellingShingle | Farida Galieva Mohamed Khalifa Zaliya Akhmetzyanova Diana Mironova Vladimir Burilov Svetlana Solovieva Igor Antipin New Supramolecular Hypoxia-Sensitive Complexes Based on Azo-Thiacalixarene Molecules supramolecular chemistry thiacalixarene hypoxia sensing host–guest complex cationic rhodamine dyes |
| title | New Supramolecular Hypoxia-Sensitive Complexes Based on Azo-Thiacalixarene |
| title_full | New Supramolecular Hypoxia-Sensitive Complexes Based on Azo-Thiacalixarene |
| title_fullStr | New Supramolecular Hypoxia-Sensitive Complexes Based on Azo-Thiacalixarene |
| title_full_unstemmed | New Supramolecular Hypoxia-Sensitive Complexes Based on Azo-Thiacalixarene |
| title_short | New Supramolecular Hypoxia-Sensitive Complexes Based on Azo-Thiacalixarene |
| title_sort | new supramolecular hypoxia sensitive complexes based on azo thiacalixarene |
| topic | supramolecular chemistry thiacalixarene hypoxia sensing host–guest complex cationic rhodamine dyes |
| url | https://www.mdpi.com/1420-3049/28/2/466 |
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